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ABSTRACT

A COORDINATION CATALYST SYSTEM USEFUL AT HIGH TEMPERATURES, E.G., 75*C., FOR MAKING ELASTOMERIC HIGH MOLECULAR WEIGHT COPOLYMERS OF ETHYLENE AND AT LEAST ONE ALPHAMONOOLEFIN OF THE FORMULA R-CH2-CH=CH2 WHEREIN R CAN BE HYDROGEN OR AN ALKYL GROUP OF 1 TO 15 CARBON ATOMS, SAID CATALYST SYSTEM CONSISTING ESSENTIALLY OF (A) TITANIUM TETRABROMINE, (B) A DIORGANOALUMINUM BROMIDE CONTAINING 1 TO 18 CARBON ATOMS, E.G., DISOBUTYLALUMINUM BROMIDE, (C) A DIORGANOMAGNESIUM COMPOUND REPRESENTED BY THE FORMULA R1R2MG WHEREIN R1 AND R2 ARE ALKYL, CYCLOALKYL, ARALYL, ALKENYL, ARYL SUBSTITUTED ALKENYL, OR CYCLOALKENYL, AND R1 AND R2 CONTAIN A TOTAL OF 8 TO 30 CARBON ATOMS, E.G., N-BUTYL-SEC-BUTYLMAGNESIUM, (D) AS A MODIFIER TO RAISE THE COPOLYMER MOLECULAR WEIGHT, AN ALIPHATIC ETHER OF THE FORMULA R&#39;&#39;OR&#34; WHEREIN R&#39;&#39; AND R&#39;&#39;&#39;&#39; REPRESENT ALKYL GROUPS EACH HAVING 2 TO 5 CARBON ATOMS, AND (E) AN INERT ORGANIC DILUENT, E.G., HEXANE, WITH THE PROVISO THAT THE RATIOS OF MAGNESIUM ATOMS TO TITANIUM ATOMS AND ALUMINUM ATOMS TO TITANIUM ATOMS IN THE CATALYST SYSTEM ARE IN ACCORDANCE WITH THE FOLLOWING RELATIONSHIPS: AI: TI=A(2-30) : 1 MINIMUM MG : TI = MMIN, =0.1351+0.15-Q MAXIMUM MG : TI = MMAX, =0.826A+0.05-Q WHERE Q IS THE CONCENTRATION OF TI (IN MILLIMOLES/LITER) IN THE REACTOR LIQUID PHASE AND RANGES FROM 0.05 TO 0.2 AND THE MOLES OF ETHER ATOM OF MAGNESIUM BEING IN THE RANGE (0.5-1.5):1. THE PREFERRED CATALYST HAS COMPONENTS IN THESE PROPORTIONS: AI:MG:ETHER:TI=6:3:3:1. IT IS PREFERRED THAT THE CATALYST BE FORMED IN SITU BY SEPARATE INTRODUCTION OF HYDROCARBON SOLUTIONS OF EACH COMPONENT, HOWEVER, CALALYST COMPONENTS CAN BE PREMIXED.

rozstlrcnrron UNITED STATES PATENT AND TRADEMARK OFFICE 'IhibliiiliQd at the request of the an") abstracts ot Defen ive Publication 1' Thu hoarding: of ouch absti ct inilic in the application as or 1y i may be purchased for St tints a Defensive Publication app! ions have not brcn examined as to the merits of alleged invention. The Patent and Trademark Office makes no assortion as to the novelty of the disclosed subject matter.

r it or owirr in accordance with the Notice of Dec f6, 1969, 869 O.G. 687. The c iucntiticd by distinctly numbered series, and are arranged chronologically. :1 0t spcciliciition, including claims and sheets of drawings contained ,7 pplications are available to the public for inspection and reproduction mot.

PUBLISHED MAY (3, 1975 T934,004 PROfiESS Allen Leroy Blancett, Camden, S.C., assignor to E. I. du Pont i c Ncmours and Company, Wilmington, Del. Filed Mar. 1, 1974, Ser. No. 447,255 Int. Cl. D06p 5/00 [1.5. Cl. 8-17 1 Sheet Drawing. 13 Pages Specification A coordination catalyst system useful at high temperatures, c.g., 75 C., for making elastorncric high molecular Weight copolymcrs 0t ethylene and at least one alphamonoolctin oi the formula R-CH -CH=CH wherein R can be hydrogen or an alkyl group of l to 15 carbon atoms, said catalyst system consisting essentially of (a) titanium tetrabromide, (b) a diorganoaluminum bromide containing 1 to [3 carbon atoms, e.g., disobutylaluminum bromide, (c) a diorganomagnesium compound represcntcd by tho l'orrnula R R Mg wherein R and R are aikyl, cycionlkyl, aralkyl, alkaryl, alkcnyl, aryi substituted alkenyl, or cycioalkenyl, and R and R contain a total of 8 to 30 carbon atoms, c.g., n-butyl-sec-butylrnagnesium, (d) as a modifier to raise the copolymer molecular weight, an aliphatic cthcr of the formula R'OR" wherein R and R" represent alkyl groups each having 2 to 5 carbon atoms, and (e) an inert organic diluent, e.g., hexane, with the proviso that the ratios of magnesium atoms to titanium atoms and aluminum atoms to titanium atoms in the catalyst system are in accordance with the following relationships:

A1:Ti= A (2-30) :1

minimum Mg 1 Ti: M 0,135A+9% maximum Mg Ti= M 0.826A-i-g8- where Q is the concentration of Ti (in millimoles/liter) in the reactor liquid phase and ranges from 0.05 to 0.2 and the moles of etherzatom of magnesium being in the range (0.5-1.5) :1. The preferred catalyst has components in these proportions: Al:Mg:Ethcr:Ti=6:3:3:1. It is preferred that the catalyst be formed in sitzz by separate introduction of hydrocarbon solutions of each component; however, catalyst components can be premixed.

A4L.BLANCETT PROCESS Filed March 1, 1974 

